Re-defining the kinetics of redox reactions on passive metal surfaces

It is known that the kinetics of redox reactions occurring on the surfaces of passive metals depend upon the properties of the passive film, ostensibly due to quantum mechanical tunnelling (QMT) of electrons and holes between the metal and the redox couple at the barrier layer/solution (bl/s) interface. In this paper, the tunnelling probability is used to inter-convert the exchange current densities for the redox reactions occurring at the bl/s interface and on the hypothetical bare metal surface. We review our previous work on combining QMT theory with the point defect model (PDM), which provides an analytical expression for the bl thickness as a function of voltage. By combining QMT theory and the PDM, we derive a modified form of the generalized Butler-Volmer equation that requires as input only the kinetic parameters for the redox reaction on the hypothetical bare surface and parameters contained in the PDM. The application of the theory is illustrated with reference to the corrosion of carbon steel in concrete pore solution, to calculating the corrosion potential of, and crack growth rate in, sensitized type 304 SS in boiling water reactor (BWR) coolant circuits, and the use of hydrogen oxidation on platinum to determine the thickness of the bl as a function of voltage and temperature. This illustrates a new, powerful technique for probing the formation of passive films on metal surfaces.

     

Chemical‐Reductant‐Free Electrochemical Deuteration Reaction using Deuterium Oxide

We report a method for the electrochemical deuteration of α,β‐unsaturated carbonyl compounds under catalyst‐ and external‐reductant‐free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O₂ evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.     

低温功率器件驱动电路实验研究

低温电力电子技术的发展日益得到重视,主要是由于功率器件(如功率MOSFET和IGBT等)在低温下表现出更好的性能,如更低的通态阻抗,更高的开关频率等.为了实验测试和充分利用功率器件在低温下的这些性能,急需寻找或设计可以在低温下稳定可靠工作的功率器件驱动电路.我们在对目前商业化的驱动芯片进行分析的基础上,从中挑选了三种在低温下进行实验,对其输出波形随温度的变化进行研究,首次发现了可以在-196℃(77K)稳定工作的驱动芯片,其驱动性能基本能够满足低温下驱动功率器件的要求,为功率器件低温特性测试及低温功率变换电路的设计奠定了坚实的基础.     

Geodesic metrics on fractals and applications to heat kernel estimates

It is well known that for a Brownian motion, if we change the medium to be inhomogeneous by a measure μ, then the new motion(the time-changed process) will diffuse according to a different metric D(·, ·).In 2009, Kigami initiated a general scheme to construct such metrics through some self-similar weight functions g on the symbolic space. In order to provide concrete models to Kigami’s theoretical construction, in this paper,we give a thorough study of his metric on two classes of fractals of pr...     

Magnetron sputtering deposition of silicon nitride on polyimide separator for high-temperature lithium-ion batteries

To date,lithium-ion batteries are becoming increasingly significant in the application of portable devices and electrical vehicles,and revolutionary progress in theoretical research and industrial application has been achieved.However,the commercial polyolefin separators with unsatisfying electrolytes affinity and poor thermal stability have extremely restricted the further application of lithium-ion batteries,especially in the high-temperature fields.In this work,magnetron sputtering deposition technique is employed to modify the commercial polyimide separator by coating silicon nitride on both sides.Magnetron sputtering deposition modified polyimide(MSD-PI)composite separator shows high thermal stability and ionic conductivity.More importantly,compared with the cells using Celgard separator,the cells with MSD-PI separator exhibit superior electrochemical performance,especially long-term cycle performance under high temperature environment,owing to the high thermal conductivity of surface Si3 N4 particles.Hence,lithium-ion batteries with MSD-PI separator are capable of improving thermal safety and capacity retention,which demonstrates that magnetron sputtering deposition technique could be regarded as a promising strategy to develop advanced organic/inorganic composite separators for high-temperature lithium-ion batteries.     

Electrical and Thermal Transport Properties of n-type Bi6Cu2Se4O6 (2BiCuSeO + 2Bi2O2Se)

New thermoelectric materials, n-type Bi₆Cu₂Se₄O₆ oxyselenides, composed of well-known BiCuSeO and Bi₂O₂Se oxyselenides, are synthesized with a simple solid-state reaction. Electrical transport properties, microstructures, and elastic properties are investigated with an emphasis on thermal transport properties. Similar to Bi₂O₂Se, it is found that the halogen-doped Bi₆Cu₂Se₄O₆ possesses n-type conducting transports, which can be improved via Br/Cl doping. Compared with BiCuSeO and Bi₂O₂Se, an extremely low thermal conductivity can be observed in Bi₆Cu₂Se₄O₆. To reveal the origin of low thermal conductivity, elastic properties, sound velocity, Grüneisen parameter, and Debye temperature are evaluated. Importantly, the calculated phonon mean free path of Bi₆Cu₂Se₄O₆ is comparable to the interlayer distance for BiO─CuSe and BiO─Se layers, which is ascribed to the strong interlayer phonon scattering. Contributing from the outstanding low thermal conductivity and improved electrical transport properties, the maximum ZT ≈0.15 at 823 K and ≈0.11 at 873K are realized in n-type Bi₆Cu₂Se_3.2Br_0.8O₆ and Bi₆Cu₂Se_3.6Cl_0.4O₆, respectively, indicating the promising thermoelectric performance in n-type Bi₆Cu₂Se₄O₆ oxyselenides.     

Guanidine-based task-specific ionic liquids as catalysts for aza-Michael addition under solvent-free conditions

An efficient and facile protocol for aza-Michael addition of aliphatic and aromatic amines to electron-deficit alkenes using [TMG][Lac] as catalyst under solvent-free conditions was established.     

An equivalent nonlinearization method for analysing response of nonlinear systems to random excitations

I.IntroductionInthelasttwodecades,theresponseofstochasticallyexcitednonlinearsystemshavebeenresearcheddeeplyandwidely.Manyexactandapproximatemethodsofpredictingtheresponseofnonlinearsystemstorandomexcitationshavebeenprop0sedl']'l21.Becauseofv4riousreasons…     

可列值随机变量序列的一个小偏差定理

本文得到了可列值随机变量序列的用不等式表示的强极限定理,即小偏差定理,包含了［１］的结果．［１］中研究的是相对于齐次Ｍａｒｋｏｖ 链的偏差,而本文允许非齐次的情形．     

可控硅外特性的研究

开发和推广可控硅特性研究的物理实验,意在启发学生对物理实验的趣味性和思考方法,让学生在实验课中根据观察到的现象和实验数据在实验课后进行分析,最后判断并得出结论.